Catalyst for vapor phase oxidation of hydrocarbons



United States Patent U.S. Cl. 252437 7 Claims ABSTRACT OF THE DISCLOSURE Useful catalysts are provided for the oxidation of gaseous hydrocarbons, as unsaturated hydrocarbons to form unsaturated aldehydes and carboxylic acids, that contain molybdenum, tellurium, a Group IIA metal, phosphorous and oxygen, for example, molybdenum oxide, tellurium oxide and an alkaline earth metal phosphate.

This is a division of application Ser. No. 483,862, filed Aug. 30, 1965 and now Patent No. 3,401,198.

This invention relates to new and useful catalysts and to a method of preparing unsaturated aldehydes and unsaturated carboxylic acids by oxidation of unsaturated hydrocar-bons at an elevated temperature, and relates more particularly to catalysts comprising a mixture of a molybdenum oxide, tellurium oxide and an alkaline earth, Group II-A, metal phosphate in a molar ratio of 100 M00 -100 TeO and l0-l00 of a II-A metal phosphate and to a method of preparing acrolein and acrylic acid, or methacrolein, and methacrylic acid by passing vapors of propylene of isobutylene and an oxygen containing gas over the catalyst at a temperature of from about 325 C. to about 550 C. The catalyst can also be designated as MomTe 10M2 20P2 20O39 120 the P being in the form of a phosphate i.e. each P is attached to 3 or 4 oxygen atoms and wherein M is a group II-A metal.

Numerous attempts have been made in the past to prepare products of higher oxidation state from hydrocarbons, especially from the normally gaseous hydrocarbons. However, all prior catalysts and procedures for oxidizing monoolefinic gaseous hydrocarbons to monoolefinically unsaturated aldehydes or monoolefinically unsaturated carboxylic acids with the same number of carbon atoms as the hydrocarbon having serious short-comings. The catalysts either have a very short active life, or they convert only a portion of the hydrocarbon to desired end groups per pass; they oxidize the hydrocarbon excessively to form high proportions of carbon monoxide or carbon dioxide or both; they are not sufliciently selective, so that the hydrocarbon molecule is attacked at both the olefinic unsaturation and at a methyl group; or the oxidation of the olefin does not proceed beyond the aldehyde stage.

It is therefore unexpected to find a catalyst having unusually long life that will convert a substantial amount, more than 50% per pass, of a gaseous monoolefin such as propylene or isobutylene to yield very high proportion of acrolein and acrylic acid or methacrolein and methacrylic acid. It is also unexpected to find a catalyst that produces a wide range of ratios of olefinic aldehyde to monoolefinically unsaturated carboxylic acid by controllable changes in reaction conditions or catalyst composition. Mol percent efiiciencies of about 15 to for the aldehyde and about 21 to 45 for the unsaturated carboxylic acid have been obtained with the catalyst and process of this invention. Usually when the efliciency for conversion of the hydrocarbon to aldehyde is high the efliciency for the conversion to acid is low and vice versa. This provides a great degree of flexibility in the process, so as to provide means for obtaining a product mix that may be needed at any particular time during commercial operation:

The reactants The essential reactants are (1) propylene or isobutylene and (2) an oxygen containing gas, which can be pure oxygen, oxygen diluted with an inert gas, oxygen enriched air or air without additional oxygen. For reasons of economy, air is the preferred oxygen containing reactant.

For the purpose of this invention the hydrocarbons which are oxidized can be defined generically by the formula wherein it is also apparent that the end products formed result from the oxidation of only one methyl group on the hydrocarbon molecule while the terminal I C Hz- C remains intact.

Stoichiometric ratios of oxygen to olefin for the purpose of this invention are 1.5 to 1. Slightly lower amounts of oxygen can be used at a sacrifice of yield. It is preferred, however, to use 33 to 66% excess oxygen. Larger excesses do not impair the yields of aldehydes and acids, but for practical considerations an excess much above would require extremely large equipment for a given production capacity.

The addition of steam into the reactor along with the hydrocarbon and oxygen containing gas is desirable but not absolutely essential. The function of steam is not clear, but it seems to reduce the amount of carbon monoxide and dioxide in the effluent gases.

Other diluent gases can be used. Surprisingly, saturated hydrocarbons such as propane are rather inert under the reaction conditions. Nitrogen or other known inert gases can be used as diluents if desired.

The catalyst and its preparation There are several methods for the preparation of the catalyst, which can be supported or unsupported. It is possible to dissolve each of the starting ingredients in water and combine them from the aqueous solutions or the ingredients can be dry blended. Because of the more uniform metal salt in water. Add the requisite amount of phosphoric acid to the II-A metal salt solution. Add the tellurium salt solution to the molybdenum salt solution and then add the lI-A metal salt-phosphoric acid mixture to the molybdenum-tellurium salt mixture. The catalyst is then dried and baked at 400 C. for about 16 hours.

Supported catalysts can be prepared by adding a dry support or an aqueous slurry thereof to the aqueous solution of catalyst or the aqueous catalyst ingredients can be added to the slurry of the support.

Alternatively a slurry of the catalyst ingredients can be prepared in water, then dried and baked. For sup ported catalysts the aqueous slurry of the catalyst ingredients can be added to an aqueous suspension of the support or vice versa, and then dried and baked.

Another method is to blend the dry ingredients of the desired particle size and then mix them thoroughly. Thorough blending and uniform particle size is desired.

Specific examples of the solution method are now set forth.

In this procedure the ingredients are precipitated on blending.

(a) Dissolve 105.96 g. of ammonium molybdate (4H O) in 300 ml. of distilled water.

(b) Dissolve 31.922 g. TeO in 80 ml. of concentrated HCl.

Add the tellurium salt solution to the ammonium molybdate solution. A precipitate forms.

(c) Dissolve 44.4 g. CaCl in 100 ml. of water and add 46.2 g. of 85% H PO Add this mixture slowly to the precipitated ammonium molybdate-TeO mixture.

Dry on a steam bath and bake for 16 hours at 400 C. Thereafter, the catalyst is ground to the desired mesh size and sieved. For supported catalysts an aqueous slurry of the support can be added to the catalyst ingredients, or vice versa, prior to drying and baking.

A catalyst containing magnesium was prepared as follows:

(a) Dissolve 105.96 g. of ammonium molybdate (4H O) in 3 ml. distilled water.

(b) Dissolve 31.922 g. TeO in 75 ml. concentrated HCl and filter if necessary.

Add the tellurium salt solution to the ammonium molybdate solution. A precipitate forms.

(0) Dissolve 81.33 g. MgCl .6H O in 80 ml. of Water and add 46.2 g. of 85 H PO Add this mixture slowly to the precipitated ammonium molybdate-TeO mixture.

Dry on a steam bath and bake for 16 hours at 400 C. Thereafter, the catalyst is ground to the desired mesh size and sieved. For supported catalysts an aqueous slurry of the support can be added to the catalyst ingredients, or vice versa, prior to drying and baking.

A supported catalyst may be prepared by adding to (c) above 240 grams of an aqueous colloidal dispersion of microspheroidal silica in a concentration of 3035% SiO (Ludox H.S.). The silica may also be added to one of the individual ingredients or (c) added to the silica dispersion.

Among the suitable supports are silica, silica containing materials, such as diatomaceous earth, kieselguhr, silicon carbide, clay, aluminum oxides and even carbon, although the latter tends to be consumed during the reaction.

The exact chemical structure of the catalysts made by the above procedures is not known, but catalysts with molar ratios of 100 Mo, l0- l00 Te and -100 of a calcium or magnesium phosphate can be used for oxidizing the monoolefinic hydrocarbon to aldehyde and/or carboxylic acid. The catalyst contains chemically bound oxygen so that the generic formula can be written as MoC m0 TeO Ca P O or magnesium or other phosphate 10-100. The phosphate can be a PO, radical, a pyrophosphate, or a polyphosphate, for example, calcium diphosphate, calcium hypophosphate, calcium metaphosphate, calcium monophosphate, calcium pyrophosphate, calcium triphosphate, magnesium phosphate, magnesium .acid phosphate, magnesium pyrophosphate, barium pyrophosphate, strontium orthophosphate, beryllium phosphate and the like. The calcium and magnesium phosphates are preferred, especially as the pyrophosphates Preferred catalysts are ones having a ratio of 75 M00 25 TeO and 25 032F207 or 75 M00 25 TeO and 25 Mg P O because they give high yields of desired products and the preferred support is silica, because of its low cost and good fluidizing characteristics.

Reaction conditions The reaction can be carried out in either a fixed or fluidized catalyst bed.

The reaction temperature can range from about 300 to 450 C. for the oxidation of propylene but the preferred "range is from about 325 to about 425 C. Below 325 C. the conversion per pass is lower and low temperature tends to produce more aldehyde than desired. Usually, a longer contact time is needed at lower temperatures to obtain the yields of desired products obtainable at higher temperatures. Above 425 C. in the propylene oxidation some of the desired end products appear to be oxidized to carbon oxides. This is much more apparent at 450 C. For isobutylene, oxidation temperatures of 375-550 are desirable with the preferred range being 300450 C.

The molar ratio of oxygen to propylene or isobutylene should be at least 2 to 1 for good conversion and yields. Some excess oxygen, 33 to 66 mol percent is even more desirable and is preferred. There is no critical upper limit as to the amount of oxygen, but when air is used as the oxygen containing gas it becomes apparent that too great an excess will require large reactors, pumping, compressing and other auxiliary equipment for any given amount of desired end product. It is therefore best to limit the amount of air to provide a 33 to 66% excess of oxygen. This range provides the largest proportion of acid, under given reaction conditions. Also, since care is needed to avoid an explosive mixture, the limiting of air aids in that direction.

The molar ratio of steam to propylene or isobutylene can range from 0 to about 5 to 7, but best results are obtained with molar ratios of about 3 to 5 per mol of olefin and for this reason are preferred.

The contact time can vary considerably in the range of about 2 to 70 seconds. Best results are obtained in a range of about 8 to 54 seconds and this range is preferred. Longer contact times usually favor the production of acid at any given temperature.

The particle size of catalyst for fixed bed operations used is from 1048 mesh. As is known, for fixed beds, the size may be of a wider range particle size. For fluid bed systems the catalyst size should be from 325 mesh (U.S. Sieve).

The reaction can be run at atmospheric pressure, in a partial vacuum or under induced pressure up to 50- p.s.i. Atmospheric pressure is preferred for fixed bed systems and a pressure of l to 100 p.s.i. for fluid bed reactions. Operation at a pressure which is below the dew point of the unsaturated acid at the reaction temperature is advantageous.

The data in the examples show that variations in percentages of unsaturated acids and aldehydes can be obtained with a single catalyst, using fixed ratio of reactants but changing the temperature and/or contact time. Further variation is obtainable by controlling the other variables in the reaction including the catalyst compositions within the limits set forth herein.

The examples are intended to illustrate the invention but not to limit it.

The examples A series of runs was made in a fixed bed reactor of a high silica (Vycor) glass tube 12 inches long and 30 mm.

outer diameter. The reactor had three inlets, one for air, one for steam and one for propylene. Three external electrically operated heating coils were wound on the reactor. One of the coils extended along the entire length of the reactor and each of the remaining coils extended only about one half the length of the reactor.

Outlet vapors were passed through a short water cooled condenser. Uncondensed gases were passed through a gas chromatograph (Perkin-Elmer model 154D) and analyzed continuously. The liquid condensate was weighed and then analyzed for acrylic acid and acrolein in the gas chromatograph.

The reactor was filled to about 90% of its capacity with 170 ml. of a catalyst made by the solution method The reaction temperature was varied as the reaction proceeded.

The table below summarizes the data obtained in these runs:

Mol percent yield M01 on propylene Mol percent percent converted eifioiency Run Temp., propylene No. C. converted Aer. AA Acr. AA

Acr. Acrolein AA= Acrylic acid.

described above, using a ratio of 100 M00 33.33 TeO and 33.33 Ca P O Empirically the catalyst is I clam):

1. A catalyst composition consisting essentially of lco sass sae ss6 600 Mo Te M P O wherein M is a group II-A and the P is present as P 0 The catalyst was not supmetal and in which the ratio of M to P ranges between ported and had a mesh size of 1018 (U.S. sieve). 20 M to P and M to P and in which each P is combined Steam at a temperature of ZOO-250 C. was first passed with from 3 to 4 atoms of oxygen as a phosphate. into the reactor. Then propylene and air were separately 2. The composition of claim 1 impregnated on a silicic fed into the stream of water vapor. This mixture then support. passed through a pre-heater and entered the reactor at 3. Acatalyst composition having the empirical formula about ZOO-250 C. The reactor was pre-heated to about Mo Te Ca P O in which the ratio of 285 C. before the gas fed was begun. Ca to P is 1 to 1 and in which the P is present as a phos- The ratio of reactants was about 2.955 mols of oxygen phate. and 4.36 mols of steam per mol of propylene. Cold con- 4. A catalyst composition having the empirical formula tact time was varied as indicated. Mo Te Mg P O in which the ratio of The reaction temperature was varied as the reaction 30 Mg to P is 1 to 1 and in which the P is present as a phosproceeded. phate.

The table below summarizes the data obtained in these 5. A catalyst consisting essentially of molybdenum runs: oxide, tellurium oxide and a Group II-A metal phosphate Mol percent yield on propylene Mol percent Contact M01 percent converted efficiency Run Temp, time, propylene No. 0. seconds converted Aer. AA Acr. AA

Acr.=Acrolein, AA=Acrylic acid.

The reactor was then filled to about of its capacity in a molar ratio of M00 10-100 TeO and l0-l00 with 170 ml. of a catalyst made by the solution method II-A metal phosphate. described above, using a ratio of 100 M00 33.33 TeO 6. A catalyst of claim 5 wherein the metal phosphate and 33.33 Mg P O Emprically the catalyst is is calcium pyrophosphate.

50 7. A catalyst of claim 5 wherein the metal phosphate 100 33.33 66.6 66.6 600 is magnesium pyrophosphate.

and the P is present as P 0 The catalyst was not sup- References Cited ported and had a mesh size of 10-18 (U.S. sieve).

Steam at a temperature of ZOO-250 C. was first passed UNITED STATES PATENTS into the reactor. Then propylene and air were separately 3,192,259 6/1965 Fetterly 252-437 XR fed into the stream of water vapor. This mixture then 3,228,890 1/1966 Eden 252 435 XR passed through a pre-heater and entered the reactor at 33622998 1/1968 Callahan et 252435 XR about ZOO-250 C. The reactor was pre-heated to about 3 1 12/1968 Eden 252437 XR before the g feed was begun- 60 PATRICK P. GARVIN, Primary Examiner.

The ratio of reactants was about 2.955 mols of oxygen and 4.36 mols of steam per mol of propylene. Cold con- US. Cl. X.R.

tact time was 45 seconds.

Y73 UNITED STATES PATE 0mm; 7 CERTIFICATE OF CORRECTIQN Patent No. 3 451 9L|.5 Dated June 2 4, 1969 Inventor(s) Jagal S. Eden It is certified that error appears in the above-identified patent -and that said Letters Patent are hereby corrected as shown below:

I Column 2 line 32, for the formula. "CHz-bread cH =c':-

Column 3, line 71, for "M00 read M00 SIGNED NN'D SEALED APR? 1970 v (SEAL) Arrest:

MEI-HI E." W, J!!- Edmrd M. Flmhqk. Omission or Paton" Aficsting Office):- 

